The present invention relates to a method for the remediation of manure-contaminated material, and more particularly to a method for the remediation of manure-contaminated material treated with chemical amendments. It also relates to producing an enriched fertilizer from the remediated manure-contaminated material.
There are known processes for treating manure-containing soil. U.S. Pat. No. 3,939,280, for example, is directed to a process for treating poultry manure with acid, formaldehyde and urea to obtain a pathogen-free product suitable as feedstuff for ruminant animals.
As stated in U.S. ""208, poultry manure has been utilized for centuries as a soil enriching material because it contains an advantageous mixture of organic protein, inorganic nitrogen, fiber and minerals. The disposal of this material, which is collected in large quantities, poses a serious problem to the poultry industry. It is customary to remove the accumulated poultry manure periodically from under the cages and transport it to a disposal area some distance away. After drying and composting the poultry manure for a period of days or weeks, it is then used as a landfill, or it is sold as a soil builder. A major use of poultry manure at the present time is as a soil enriching agent, based on its inherent phosphorus content.
According to the U.S. ""280 invention, there is provided a process which comprises four critical steps. In step 1, to the poultry manure as collected in the poultry raising operation, there is added an amount of acid capable of adjusting the pH of the poultry manure to be less than 7.0, preferably about 5.5 to 6.0. Formaldehyde, or a substance that releases formaldehyde, such as paraformaldehyde, is added in step 2 and is mixed in the poultry manure, before or after step 1, to kill the bacteria present therein. As the third critical step in the process, there is added from about 1 to about 20 weight percent of urea, preferably about 2 to 10 weight percent, based on the weight of poultry manure, calculated as having zero percent moisture. The final critical step of the process is drying the product of step C to a condition suitable for storage, packaging and use, generally to a moisture content of less than 15 weight percent, preferably about 10.+xe2x88x92.5 weight percent. This final drying is conducted at a temperature below the melting point of urea, i.e., 132.degree.C.
U.S. Pat. No. 5,928,403 relates to treating poultry manure in the growing location with alum in an amount of from about 0.15 to about 9.25 pounds per bird raised. The alum-treated manure may also be used as an agricultural fertilizer.
The invention of U.S. ""403 is predicated on the discovery that treatment of poultry litter with the aluminum sulfate compound, alum, dramatically reduces ammonia volatilization from the litter. Results also indicate that alum, ferrous sulfate and calcium hydroxide effectively precipitate soluble phosphorus when added to litter, thereby reducing soluble phosphorus levels. Poultry litter is composed of a mixture of bedding material, manure, spilled food and feathers.
A need therefore exists for a method of remediation which will overcome problems associated with the above described prior art methods.
Applicants have met the above-described existing needs and have overcome the above-described prior art problems through the invention set forth herein.
Accordingly, a method is hereby provided for remediating manure-contaminated material. The method of the present invention comprises providing a mass of manure-contaminated material including in situ-formed bacteria and nitrogen-containing materials. The mass of manure-contaminated material is acidified to a pH of not more than about 7.0 without (a) destroying a substantial portion of said active bacteria, and/or (b) without liberating a substantial portion of said nitrogen-containing materials. Then, the acidified manure-contaminated material is particularized, preferably microenfractionated, as hereinafter described. The particularized, acidified manure-contaminated material is treated with at least one chemical amendment to form a treated particularized manure-contaminated material. Preferably, the microenfractionated, acidified manure-contaminated material is treated with at least one nutrient.
Preferably, acidifying of the mass of manure-contaminated material comprises neutralization. The mass of manure-contaminated material is preferably acidified with sulfuric acid and/or phosphoric acid and/or citric acid.
In a preferred form of this invention, the average size of the particularized, acidified manure-contaminated material is substantially reduced. Moreover, when the mass of manure-contaminated material undergoes microenfractionation, the average size of the particularized, acidified manure-contaminated material is substantially reduced as hereinafter described. Furthermore, the average surface area of the particularized, acidified manure-contaminated material is substantially increased. And, when the mass of manure-contaminated material undergoes microenfractionation, the surface area of the particularized, acidified manure-contaminated material is substantially increased as hereinafter described.
The amount of active bacteria, which is present in the mass of acidified manure-contaminated material, is substantially increased as compared to the amount of active bacteria which is present in said mass of manure-contaminated material. And, the amount of nitrogen-containing materials which are present in said mass of acidified manure-contaminated material as compared to the amount of nitrogen-containing materials which are present in said mass of manure-contaminated material.
Preferably, the chemical amendment comprises at least one nutrient. Additionally, the chemical amendment can be configured to activate the active bacteria so that subject method will proceed more expeditiously. Thus, in a preferred embodiment of this invention, the treated particularized manure-contaminated material comprises a fertilizer.
In one form of the invention, a method of using an apparatus is provided for the accelerated remediation of treated contaminated material. Treating of the contaminated material with at least one chemical amendment, with or without at least one biological amendment, can occur prior to, and/or during, and/or subsequent to, microenfractionating of the contaminated material. The chemical amendment can be at least one chemical reducing agent with or without at least one chemical oxidizing agent. For example, a contaminated material can be treated with at least one chemical amendment comprising a chemical reducing and/or oxidizing agent to form a treated contaminated material prior to microenfractionation of thereof. Then, an air stream is generated at a velocity sufficient for entraining the treated contaminated material therein, and the treated contaminated material is entrained in the air stream, and the treated contaminated material is microenfractionated under conditions sufficient to form a microenfractionated treated contaminated material such that subsequent accelerated remediation is provided under conditions sufficient for conducting said accelerated remediation. Alternatively, the chemical amendment(s) can be added during, or subsequent to, microenfractionating of the contaminated material. In any of the above-described methods, the accelerated remediation of the treated contaminated material can be facilitated.
The chemical amendment can also comprise at least one chemical reducing agent which is in the form of a liquid or a solid, preferably an aqueous solution, which is capable of acting as a chemical reducing agent for remediation or bioremediation purposes, particularly in the microenfractionation of contaminated materials of the present invention. These types of chemical amendments are particularly useful in the dehalogenation of halogenated hydrocarbons such as the difficult to remediate chlorinated hydrocarbons.
The chemical amendment of this invention can comprise a chemical reducing agent. Preferably, the chemical reducing agent comprises a metallic reducing agent. Preferably, the metallic reducing agent comprises a zero valent metallic compound. More preferably, the metallic reducing agent is a zero valent metallic compound comprising iron, zinc, tin, aluminum, manganese or other similar zero valent metallic compounds. Most preferably, the chemical reducing agent comprises a zero valent iron compound.
An activating agent can also be added to the chemical reducing agent to make the remediation with the chemical reducing agent more effective and/or efficient. Such activating agents are typically acidic activating agents, preferably organic acid acidic activating agents such as acetic acid, or inorganic acidic materials such as hydrochloric acid, phosphoric acid, or nitric acid. Other acidic activating agents may include aliphatic alpha-hydroxycarboxylic acids of the type RCHOHCOOH and the corresponding beta-hydroxycarboxylic acids RCHOHCH2COOH, complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrolotriacetic acid (NTA) and diethylenediamine-pentaacetic acid (DPTA) and amines, hydroxyl containing amines such as mono-, di- and triethanolamine and diamines, triamines, polyamines having complexing properties. Exemplary alpha- and beta-hydroxy carboxylic acids are glycolic acid, lactic acid, glyceric acid, xcex1,xcex2-dihydroxybutyric acid, xcex1-hydroxy-butyric acid, xcex1-hydroxy-isobutyric acid, xcex1-hydroxy-n-valeric acid, xcex1-hydroxy-isovaleric acid, xcex2-hydroxy butyric acid, xcex1-hydroxy-isobutyric acid, xcex2-hydroxy-n-valeric acid, xcex2-hydroxy isovaleric acid, erythronic acid, threonic acid, trihydroxy-isobutyric acid and saccharinic acids and aldonic acids, such as gluconic acid, galactoni acid, talonic acid, mannonic acid, arabonic acid, ribonic acid, xylonic acid, lyxonic acid, gulonic acid, idonic acid, altronic acid, allonic acid, ethenyl glycolic acid, and xcex2-hydroxy-isocrotonic acid. Also useful are organic acids having two or more carboxylic groups, and no or from one to ten hydroxyle groups, such as oxalic acid, malonic acid, tartaric acid, malonic acid, tartaric acid, malic acid, and citric acid, ethyl malonic acid, succinic acid, isosuccinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, maleic acid, fumaric acid, glutaconic acid, citramalic acid, trihydroxy glutaric acid, tetrahydroxy adipic acid, dihydroxy maleic acid, mucie acud, mannosaccharic acid, idosaccharic acid, talomucie acid, tricarballylic acid, aconitic acid, and dihydroxy tartaric acid.
The chemical amendment can also comprise at least one chemical oxidizing agent which is in the form of a liquid or a solid, preferably an aqueous solution. Preferably, the chemical oxidizing agent can comprise a peroxide, a permanganate, a nitrate, a nitrite, a peroxydisulfate, a perchlorate, a sulfate, chlorate, a hypochlorite, an iodate, a trioxide, a peroxybenzoic acid, an oxide, an iodic acid, a nitric acid, a periodic acid, a peracetic acid, a hydantoin, a triazinetrione, a hydroxide, a percarbonate, a superoxide, an isocyanate, an isocyanic acid, a bromanate, a biiodate, a bromate, a bromate-bromide, a molybdic acid, a dichromate, a chromate, a periodate, a chlorite, an iodate, or a perborate. More preferably, the chemical amendment can comprise any one of the following: aluminum nitrate, ammonium dichromate, ammonium nitrate, ammonium peroxydisulfate, ammonium permanganate, aquaquant sulfate, ammonium perchlorate, microquant sulfate, ammonium peroxydisulfate, spectroquant nitrate, barium bromate, barium chlorate, barium nitrate, barium perchlorate, barium permanganate, barium peroxide, cadmium nitrate, 1-bromo-3chloro-5,5 dimenthylhydantoin, bismuth nitrate, calcium hypochlorite, calcium iodate, calcium nitrate, ceric ammonium nitrate, ceric sulfate, calcium chlorate, calcium chlorite, calcium hypochlorite, calcium perchlorate, calcium permanganate, calcium peroxide, cerous nitrate, chloric acid, chromium trioxide, chromium nitrate, cobalt nitrate, copper chlorate, cupric nitrate, halane (1,3, dichloro-5,5dimenthylhydandoin),3-chloroperoxybenzoic acid, cobalt nitrate, ferric nitrate, hydrogen peroxide, guanidine nitrate, iodic acid, lanthanum nitrate, lead dioxide, lead nitrate, lead oxide, lead perchlorate, lithium nitrate, lithium perchlorate, lithium hypochlorite, lithium chlorate, lithium peroxide lithium, perchlorate, magnesium bromate, magnesium chlorate, magnesium peroxide, magnesium nitrate, mercuric nitrate, mercurous nitrate, mercurous chlorate, manganese dioxide, mono-(trichloro)-tetra-(monopotassium dichloro)-penta-xcex1-triazinetrione, magnesium perchlorate, nitric acid, nickel nitrate, mercurous nitrate, periodic acid, peracetic acid, perchloric acid solutions, Class II and III (depending upon centration), potassium peroxide, potassium superoxide, potassium biiodate, potassium bromate, potassium bromate-bromide, phosphomolybdic acid, phenylmercuric nitrate, potassium hydroxide, potassium iodate, potassium dichromate, potassium nitrate, potassium nitrite, potassium chromate, potassium dichloro-xcex2-triazinetrione (potassium dichloroisocyanate), potassium dichromate, potassium chlorate, potassium percarbonate, potassium nitrate, potassium perchlorate, potassium periodate, potassium permanganate, potassium persulfate, silver peroxide, sodium bromate, sodium carbonate peroxide, sodium dichloro-xcex2-triazinetrione (sodium dichloroisocyanate) silver nitrate, silver oxide, silver perchlorate, sodium chlorite, sodium chlorate, sodium nitrate, sodium iodate, sodium dichromate, sodium nitrate, sodium perborate, sodium perborate (anhydrous) sodium perchlorate, sodium percarbonate, sodium perchlorate monohydrate, sodium periodate, sodium nitrite, sodium persulfate, sodium permanganate, sodium peroxide, strontium nitrate, strontium perchlorate, strontium peroxide, thorium nitrate, trichloroisocyanic acid, zinc nitrate, thallic nitrate, uranyl nitrate, urea peroxide, yttrium nitrate, zinc bromanate, zinc chlorate, zinc permanganate, and zinc peroxide.
The contaminated material can comprise nitrated and/or chlorinated hydrocarbons including nitrated and/or chlorinated polycyclic materials, nitrated and/or chlorinated heterocyclic materials, and nitrated and/or chlorinated aliphatic materials. Exemplary contaminated compounds include chlorinated pesticides, TNT, and RDX.
Preferably, the accelerated remediation reaction is conducted aerobically or abiotically, and more preferably by an in situ abiotic process. The reaction can also be conducted methanogenically.
Generally, the means for generating a treated contaminated material entraining air stream at a predetermined velocity comprises an elongate drum having a longitudinal axis, first and second end portions, and a center portion. The drum is rotatable about its longitudinal axis at a predetermined rotational speed, and means extending outwardly from the drum are provided for generating the treated contaminated material entraining air stream. Preferably, the treated contaminated material entraining air stream comprises a plurality of air currents, and the air current generating means comprises a plurality of paddles extending outwardly from the cylindrical outer surface of the drum. Typically, each paddle comprises a base portion connected to the drum, and a blade portion. Each blade portion has a major surface oriented for generating at least one the air current having a sufficient velocity for entraining and transporting treated contaminated material upwardly of the rotating drum when the drum is rotated at the predetermined rotational velocity.
The treated contaminated material entraining air stream preferably comprises a plurality of intersecting air currents. Each of the intersecting air currents has a sufficient velocity for entraining and transporting a portion of the treated contaminated material upwardly of the air stream generating means. More specifically, the means for generating a plurality of intersecting air currents comprises a plurality of end paddles extending radially outwardly from the first and second end portions of the drum. Each end paddle can comprise a base portion connected to the drum and a blade portion. In this instance, the blade portion has a major surface oriented relative to the drum for generating an air current directed upwardly of the drum and transversely toward the center portion of the drum when the drum is rotated at the predetermined rotational speed. It also has a plurality of center paddles extending radially outwardly from the center portion of the cylindrical outer surface. Each center paddle comprises a base portion connected to the drum, and a blade portion having first and second major surfaces. The first and second major surfaces are oriented relative to the drum for generating an air current directed upwardly and rearwardly of, and transversely toward the first and second end portions of the drum respectively when the drum is rotated at the predetermined rotational speed. In use, the air currents generated by the end and center paddles intersect and combine to form the treated contaminated material entraining air stream for microenfractionating the treated contaminated material.
In a preferred embodiment, the treated contaminated material entraining air stream comprises a vortex-type air stream which transports the entrained treated contaminated material in a generally circular path. In this case, the end and center paddles can extend radially outwardly from the drum so that they are arranged in a plurality of helical longitudinal row. Also, the drum can further comprise first and second transition portions disposed between the center portion and the first and second end portions respectively. The first and second transition portions of the drums having a plurality of end paddles and a plurality of center paddles extending radially outwardly therefrom.
In another form of the invention, a method of accelerated remediation of treated contaminated material is provided. This method comprises the steps of (a) treating the treated contaminated material with chemical biological amendments for facilitating accelerated remediation thereof, (b) providing an entraining air stream having a sufficient velocity for entraining the treated contaminated material therein, (c) entraining the treated contaminated material in the air stream, (d) microenfractionating the treated contaminated material, and (e) discharging the microenfractionated treated contaminated material from the air stream so that the treated contaminated material will be acceleratedly remediated. The microenfractionating step preferably comprises homogenization and aeration of the treated contaminated material. The entraining air stream preferably comprises providing an entraining air stream including a plurality of upwardly and transversely flowing, intersecting air currents, and more preferably comprises a vortex-like entraining air stream. Typically, the step of providing an entraining air stream includes the step of rotating a drum assembly at a rotational speed sufficient for generating the entraining air stream. The drum assembly can include means for generating this plurality of intersecting air currents when the drum assembly is rotated.
In one preferred method, the treated contaminated material is contaminated with a hydrocarbon material, and the accelerated remediation of the treated contaminated material comprises accelerated chain scission of the hydrocarbon material. In another case, when the treated contaminated material is contaminated with hydrocarbon material, the accelerated remediation, typically employing chemical reduction. If the hydrocarbon contaminant is halogenated, a halogen will also be produced. A further instance is where the treated contaminated material is contaminated with hydrocarbon material, and the accelerated remediation comprises reduction of the total hydrocarbon material in the treated contaminated material.
In general, at least about 70%, preferably at least about 80%, more preferably at least about 90%, and most preferably at least about 95% of the accelerated remediation of the treated contaminated material is completed within 150 days, preferably within 120 days, more preferably within 90 days, and most preferably within 60 days. Moreover, the volume of treated contaminated material which is acceleratedly remediately treated by the method of the present invention is generally at least about 1500 cubic yards, preferably at least about 2000 cubic yards more preferably at least about 2500 cubic yards, most preferably at least about 3000 cubic yards, per day per apparatus. This is particularly significant in the case of chlorinated contaminates since most prior art systems cannot remediate these compounds even after years of trying to treat same.
The method of the subject invention produces high surface area treated contaminated microenfractionated material. The surface area of the treated contaminated non-microenfractionated material can be increased, after the microenfractionating step, as compared to the surface area of the treated contaminated non-microenfractionated material, by a factor of at least about 1xc3x97106, preferably at least about 2xc3x97106, more preferably at least about 3.5xc3x97106, and most preferably at least about 5xc3x97106. More specifically, the subject method can further include the step of discharging the microenfractionated treated contaminated material from the air stream and redistributing it throughout a soil matrix. In this manner, the surface area of the microenfractionated treated contaminated material is substantially increased. This is especially important when dealing with clay type soils.
Most prior art remediation processes cannot be conducted at ambient temperatures below 10 degrees C. However, when the method of the subject invention is employed, the aforementioned high degree of accelerated remediation can be maintained at an average ambient temperature which is not more than about 10 degrees C., preferably not more than about 7 degrees C., more preferably not more than about 3 degrees C., and most preferably not more than about 1 degree C.
One reason why the accelerated remediation of this invention can be conducted at the low ambient temperature conditions described in the preceding paragraph herein, is that the subject reaction is generates a more substantial amount of exothermic heat than known prior art remediation processes. Thus, the accelerated remediation is preferably conducted at an exothermic temperature measured within the contaminated material of at least about 5 degrees, and more preferably at least about 10 degrees, higher than an average ambient air temperatures of from about zero up to about 10 degrees C.
As for the treatment of the contaminated material with the chemical amendments, it is preferred that they are dispersed throughout the redistributed microenfractionated treated contaminated material thereby facilitating accelerated remediation.
Other preferred embodiments of the subject method include (a) locating an impervious undercover below the treated contaminated material prior to the microenfractionating step thereby preventing the chemical amendments from leaching into soil underlying the treated contaminated material, and (b) a cover over the microenfractionated treated contaminated material, the cover allowing substantial solar radiation to pass therethrough and into the microenfractionated treated contaminated material, thereby facilitating the accelerated remediation and preventing moisture from soaking the microenfractionated treated contaminated material and to prevent moisture evaporation from the microenfractionated treated contaminated material.